EP0361675A1 - Compositions de polyisocyanate - Google Patents

Compositions de polyisocyanate Download PDF

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Publication number
EP0361675A1
EP0361675A1 EP89308570A EP89308570A EP0361675A1 EP 0361675 A1 EP0361675 A1 EP 0361675A1 EP 89308570 A EP89308570 A EP 89308570A EP 89308570 A EP89308570 A EP 89308570A EP 0361675 A1 EP0361675 A1 EP 0361675A1
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EP
European Patent Office
Prior art keywords
uretonimine
polyisocyanate
polyisocyanate composition
composition according
carbodiimide modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP89308570A
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German (de)
English (en)
Inventor
Edward Francis Cassidy
Jan Willem Leenslag
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Publication date
Priority claimed from GB888821186A external-priority patent/GB8821186D0/en
Priority claimed from GB898900855A external-priority patent/GB8900855D0/en
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0361675A1 publication Critical patent/EP0361675A1/fr
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C08G18/503—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups being in latent form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8054—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes

Definitions

  • This invention relates to polyisocyanate compositions and to their use in the manufacture of polyurethane and other poly­meric materials.
  • polyurethane materials which may be flexible or rigid, foamed or unfoamed, are produced on a large scale by reacting polyisocyanates with low and/or high molecular weight poly­hydroxy compounds.
  • polyurea products are obtained by reacting polyisocyanates with polyamines.
  • the organic polyisocyanates used in these reactions include simple aliphatic and aromatic diisocyanates but also more complex derivatives thereof containing urethane, urea, allophanate, biuret, carbodiimide, uretonimine or isocyanurate residues.
  • these modified polyisocyanates are used in order to provide a liquid form of a normally solid isocyanate compound, for example the so-called MDI variants. In other cases, they are used to provide other desired technical effects.
  • polyisocyanate compositions may be obtained by reacting uretonimine and/or carbodiimide modified polyisocyanates with carboxylic acids.
  • the present invention provides a polyisocyanate composition which is the product of reacting a uretonimine and/or carbodiimide modified polyisocyanate with a carboxylic acid.
  • polyisocyanates containing carbodiimide and/or uretonimine groups and methods for their preparation have been fully described in the prior art.
  • these modified poly­isocyanates are obtained by contacting an organic poly­isocyanate such as diphenylmethane diisocyanate (MDI) with a carbodiimidisation catalyst (commonly a phosphorus compound) to form a carbodiimide modified polyisocyanate which reacts with further polyisocyanate forming a uretonimine modified poly­isocyanate, the carbodiimide/uretonimine ratio varying with temperature.
  • MDI diphenylmethane diisocyanate
  • a carbodiimidisation catalyst commonly a phosphorus compound
  • the level of uretonimine and/or carbodiimide modification of the polyisocyanates used in accordance with the invention may vary over a wide range.
  • Organic polyisocyanates which may be used in the preparation of the uretonimine and/or carbodiimide modified polyisocyanates include aliphatic, cycloaliphatic and araliphatic poly­isocyanates, for example hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-­4,4′-diisocyanate and p-xylylene diisocyanate.
  • aliphatic, cycloaliphatic and araliphatic poly­isocyanates for example hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-­4,4′-diisocyanate and p-xylylene diisocyanate.
  • the preferred polyisocyanates are the aromatic polyisocyanates, 1,5-naphthylene diisocyanate and especially the available MDI isomers, that is to say 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and mixtures thereof with each other or with other polyisocyanates.
  • Carboxylic acids which may be used in the preparation of the polyisocyanate compositions of the invention may contain one or more carboxylic acid groups per molecule and may be polymeric or non-polymeric in structure. Suitable acids include simple aliphatic or aromatic mono- or dicarboxylic acids. Polycarboxylic acids which are liquids at the temperatures used for reaction with the uretonimine and/or carbodiimide modified polyisocyanate, that is to say at temperatures of 120° C or below, are preferred.
  • liquid polycarboxylic acids examples include the commercially available dimer acids obtained by the dimerisation of unsaturated fatty acids as well as carboxy terminated polymers, for example polynitriles, polyesters or polyethers.
  • Carboxy terminated polyesters may be obtained in known manner by reacting polyhydric alcohols, for example glycols, with a stoichiometric excess of a polycarboxylic acid or anhydride thereof.
  • Carboxy terminated polyethers may be obtained by reacting a polyether polyol with a polycarboxylic acid or anhydride, a large excess of the acid component being used when it is desired to minimise chain extension.
  • each chain end carries a single carboxy group
  • a reaction product of a polyether polyol and an excess of a dicarboxylic anhydride there may be used polyethers wherein each chain end carries two or more carboxy groups, for example reaction products of a polyether polyol and a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride.
  • acids or acid anhydrides such as maleic anhydride, phthalic anhydride, trimellitic anhydride or pyromellitic dianhydride.
  • Suitable polyoxyalkylene polyols are well known in the art and may be based on propylene oxide, butylene oxide, ethylene oxide, tetrahydrofuran and combinations thereof. Polyoxypropylene and poly­(oxypropylene/oxyethylene) polyols are generally preferred.
  • Reaction between the uretonimine and/or carbodiimide modified polyisocyanate and the carboxylic acid is preferably effected under such conditions that reaction between the carboxylic acid and the free isocyanate groups of the polyisocyanate as well as reactions between the free isocyanate groups are minimised.
  • Such conditions include the use of reaction temperatures below 120°C, preferably not exceeding 100°C with an initial ratio of uretonimine/carbodiimide to carboxy groups of at least 1:1 and with no catalyst present. Where it is desired that reaction should also take place between carboxy groups and some of the isocyanate groups, or between the free isocyanate groups, higher reaction temperatures and/or suitable catalysts, for example phospholene oxides, may be used.
  • polyisocyanate compositions of the invention derived from uretonimine and/or carbodiimide modified polyisocyanates based on diisocyanates of the formula R(NCO)2, wherein R represents a divalent hydrocarbon radical, for example methylene-bis-phenylene, contain terminal groups of the formula : wherein n is 0 (in the case of a carbodiimide based material) or 1 (in the case of a uretonimine based material).
  • polyisocyanate compositions of the invention have relatively low viscosities because of the very low degree of chain extension which takes place during their preparation. This is in marked contrast to some of the modified polyisocyanates of the prior art which are prepared from such reactants and under such conditions that a significant degree of chain extension is unavoidable.
  • compositions of the invention may be reacted with active hydrogen containing materials, using known techniques, to form polyurethane, polyurea and other useful polymeric materials.
  • active hydrogen containing materials such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bi
  • a liquid stream comprising a polyisocyanate composition of the invention may be impingement mixed with a second liquid stream typically containing an isocyanate reactive softblock component, for example a polyol, polyamine, imino-functional compound or enamine compound having an equivalent weight of at least 750 and an isocyanate-reactive chain extender, for example an aromatic diamine having a molecular weight of 100 to 400 such as a diethyl toluene diamine.
  • an isocyanate reactive softblock component for example a polyol, polyamine, imino-functional compound or enamine compound having an equivalent weight of at least 750
  • an isocyanate-reactive chain extender for example an aromatic diamine having a molecular weight of 100 to 400 such as a diethyl toluene diamine.
  • Examples 1-10 The invention is illustrated but not limited by the following Examples 1-10. Examples 11-14 have been included for comparative purposes. In the Examples, all parts and percentages are expressed on a weight basis. All elastomer properties were measured in accordance with standard methods.
  • Prepolymer 1 having an isocyanate content of 26.51 % by weight, was prepared by reacting 15 parts of a 3600 Mw carboxylic acid-ended difunctional liquid nitrile rubber (HYCAR R 1300 X 8, B.F. Goodrich Co.) with 85 parts of a 20 % uretonimine/carbodiimide modified 4,4′-diphenylmethane diisocyanate having an NCO content of 29.5 %. The reaction was carried out at 100°C for 2 hours.
  • Prepolymer 2 having an isocyanate content of 26 % by weight, was prepared by reacting 15 parts of a 600 Mw carboxylic acid-ended difunctional unsaturated fatty acid dimer (EMPOL R 1009, Unichema) with 85 parts of a 20 % uretonimine/ carbodiimide modified 4,4′-diphenyl methane diisocyanate. The reaction was carried out at 100°C for 2 hours.
  • EMPOL R 1009 carboxylic acid-ended difunctional unsaturated fatty acid dimer
  • Prepolymer 3 having an isocyanate content of 25.19 % by weight, was prepared by reacting 13 parts of a 600 Mw carboxylic acid-ended difunctional unsaturated fatty acid dimer (EMPOL R 1009, Unichema.) with 87 parts of a 20 % uretonimine/­carbodiimide modified 4,4′-diphenylmethane diisocyanate. The reaction was carried out at 100°C for 2 hours.
  • EMPOL R 1009 carboxylic acid-ended difunctional unsaturated fatty acid dimer
  • Prepolymer 4 having an isocyanate content of 23.57 % by weight, was prepared by reacting 20 parts of a 3600 Mw carboxylic acid-ended difunctional liquid nitrile rubber (HYCAR R 1300 X 8, B.F. Goodrich Co.) with 80 parts of a 20 % uretonimine/carbodiimide modified 4,4′-diphenylmethane diisocyanate. The reaction was carried out at 100°C for 2 hours.
  • Prepolymer 5 having an isocyanate content of 23.57 % by weight, was prepared by reacting 20 parts of a 2200 Mw carboxylic acid-ended polyoxypropylene glycol (maleic anhydride capped PPG 2000) with 80 parts of a 20 % uretonimine/­carbodiimide modified 4,4′-diphenylmethane diisocyanate. The reaction was carried out at 100°C for 2 hours.
  • the carboxy-terminated polyether used in this Example was prepared as follows :
  • Polyurea elastomers were prepared using the reaction injection moulding (RIM) process by injecting two liquid streams, maintained at ca. 40°C, of polyisocyanate and polyamine, under pressure (ca. 200 bar), into a closed mould for subsequent reaction.
  • the steel mould employed was of the dimensions 30 cm X 30 cm X 3 mm, and was maintained at ca. 90°C.
  • the elastomers were removed from the mould 20 seconds after injection, and were post thermally treated by placing them in a vented oven maintained at ca. 160°C for ca. 30 minutes. Physical properties of the elastomers were measured within 3 days of their post thermal treatment.
  • Polyurea elastomer was prepared, using the RIM process previously described, by reacting 41.52 parts of prepolymer 4 with 40.94 parts of a 5000 Mw polyoxypropylene triamine and 17.54 parts of an 80/20 isomer mixture of 2,4- and 2,6-­diethyltoluene diamines (DETDA).
  • DETDA 2,4- and 2,6-­diethyltoluene diamines
  • Polyurea elastomer 2 was prepared by reacting 43.82 parts of prepolymer 4 with 39.33 parts of the polyether triamine used in Example 6 and 16.85 parts of DETDA.
  • Polyurea elastomer 3 was prepared by reacting 41.52 parts of prepolymer 5 with 40.94 parts of the polyether triamine used in Example 6 and 17.54 parts of DETDA.
  • Polyurea elastomer 4 was prepared by reacting 43.82 parts of prepolymer 5 with 39.33 parts of the polyether triamine used in Example 6 and 16.85 parts of DETDA.
  • PHYSICAL PROPERTIES OF POLYUREA ELASTOMERS POLYUREA ELASTOMER : 1 2 3 4 FLEXURAL MODULUS (MPa) : 435 440 600 651 DENSITY (KG/M3) : 1074 1074 1100 1120 HARDNESS (SHORE D) : 61 64 67 67 TENSILE STRENGTH (KPa) : 23707 28891 36484 33636 ELONGATION (%) : 188 186 161 125 HEAT SAG (mm) 30′ : 4.5 4.5 2.0 1.5 [150 mm O/H, 160°C] 60′ : 12.0 11.0 3.5 6.0
  • CLTE (alpha.10 ⁇ 6/°C) 172 124 135 117 IMPACT (J) +20°
  • Prepolymer 6 having an isocyanate content of 23.5 % by weight, was prepared by reacting 25 parts of a 2000 MW polyoxypropylene glycol with 65 parts of an 80/20 mixture of 4,4′- and 2,4′-diphenylmethane diisocyanates. 10.0 parts of a uretonimine/carbodiimide modified diphenylmethane diisocyanate having an isocyanate content of 29.5 % by weight was stirred into this prepolymer after preparation.
  • Prepolymer 7 having an isocyanate content of 20.92 % by weight, was prepared by reacting 33.88 parts of a 5000 MW polyoxypropylene triol with 56.12 parts of an 80/20 mixture of 4,4′- and 2,4′-diphenylmethane diisocyanates. 10.0 parts of a uretonimine/ carbodiimide modified diphenylmethane diisocyanate having an isocyanate content of 29.5 % by weight was stirred into this prepolymer after preparation.
  • Polyurea elastomer 5 was prepared according to the RIM process previously described. It was prepared by reacting 39.39 parts of prepolymer 6 with 44.24 parts of the polyether triamine used in Example 6 and 16.37 parts of DETDA.
  • PHYSICAL PROPERTIES OF ELASTOMERS POLYUREA ELASTOMER : 5 6 FLEXURAL MODULUS (MPa) : 359 351 DENSITY (KG/M3) : 1088 1103 HARDNESS (SHORE D) : 58 59 TENSILE STRENGTH (KPa) : 25000 28652 ELONGATION (%) : 300 260 HEAT SAG (mm) 30′ : 5.0 10.0 [150 mm O/H, 160°C] 60′ : 16.0 28.0 CLTE (alpha.10 ⁇ 6/°C) : 132 130 IMPACT (J) +20°C : 47 100 [FALLING DART] -20°C : 38 46
  • All elastomers prepared according to the present invention showed higher modulus and improved modulus/impact combinations than those of the comparative Examples. Also, elastomers prepared according to the present invention showed improved thermal stability over those of the comparative Examples.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP89308570A 1988-09-09 1989-08-24 Compositions de polyisocyanate Ceased EP0361675A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8821186 1988-09-09
GB888821186A GB8821186D0 (en) 1988-09-09 1988-09-09 Compositions of matter
GB8900855 1989-01-16
GB898900855A GB8900855D0 (en) 1989-01-16 1989-01-16 Polyisocyanate compositions

Publications (1)

Publication Number Publication Date
EP0361675A1 true EP0361675A1 (fr) 1990-04-04

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP89308570A Ceased EP0361675A1 (fr) 1988-09-09 1989-08-24 Compositions de polyisocyanate

Country Status (7)

Country Link
US (1) US5081211A (fr)
EP (1) EP0361675A1 (fr)
JP (1) JPH02107627A (fr)
KR (1) KR900004862A (fr)
AU (1) AU4082989A (fr)
DK (1) DK442689A (fr)
NZ (1) NZ230314A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1088840A1 (fr) * 1999-10-01 2001-04-04 Basf Aktiengesellschaft Masses à couler de polyuréthane transparente, stérilisables à la vapeur, non-cytotoxiques, leur procédé de préparation et leur utilisation, en particulier pour des articles médicaux
EP1088839A1 (fr) * 1999-10-01 2001-04-04 Basf Aktiengesellschaft Masses à couler de polyuréthane transparente, stérilisables à la vapeur, non-cytotoxiques, leur procédé de préparation et leur utilisation, en particulier pour des articles médicaux
EP2998331A1 (fr) * 2014-09-17 2016-03-23 Construction Research & Technology GmbH Polymère organique durcissable comprenant au moins une unité d'acylurée, sa préparation et son utilisation

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Publication number Priority date Publication date Assignee Title
DE3643241C2 (fr) * 1985-03-29 1990-07-26 Nisshinbo Industries, Inc., Tokio/Tokyo, Jp
US5298593A (en) * 1991-06-25 1994-03-29 Mitsubishi Petrochemical Company, Ltd. Method of producing thermotropic liquid crystalline polyester
GB9125918D0 (en) * 1991-12-05 1992-02-05 Ici Plc Reaction system for preparing polyurethane/polyurea
US5216035A (en) * 1992-06-22 1993-06-01 Basf Corporation Water-blown polyurethane integral skin foam
US5284880A (en) * 1993-04-15 1994-02-08 Basf Corporation Water-blown polyurethane integral skin foam
DE60014435T2 (de) * 1999-12-10 2006-03-02 Dow Global Technologies, Inc., Midland Gussblasenfreier polyharnstoff und verfahren zu seiner herstellung
DE102004015985A1 (de) * 2004-04-01 2005-10-20 Bayer Materialscience Ag Verfärbungsstabile Polyetherallophanate
EP1754721A1 (fr) * 2005-08-16 2007-02-21 Sika Technology AG Agents résistants aux chocs terminés par des groupes d'amine, leurs dérivés et leur utilisation.
US8476330B2 (en) * 2007-07-13 2013-07-02 Momentive Performance Materials Inc. Polyurethane foam containing synergistic surfactant combinations and process for making same

Citations (6)

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FR2259119A1 (fr) * 1974-01-28 1975-08-22 Basf Ag
US4077989A (en) * 1974-07-30 1978-03-07 Bayer Aktiengesellschaft Process for the production of modified polyisocyanates
US4260718A (en) * 1979-12-18 1981-04-07 The Upjohn Company Modified carbodiimide-containing polyisocyanates and glassy polyurethanes therefrom
EP0032011A1 (fr) * 1980-01-02 1981-07-15 Imperial Chemical Industries Plc Mélanges d'isocyanates modifiés
EP0099519A1 (fr) * 1982-07-20 1984-02-01 Bayer Ag Procédé de préparation de matières plastiques à base de polyisocyanates
EP0287947A2 (fr) * 1987-04-24 1988-10-26 Bayer Ag Procédé pour la préparation de revêtements contenant des groupes hydantoine par réaction de composés contenant des groupes carbodiimide avec des acides carboxyliques insaturés

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DE2013787A1 (de) * 1970-03-23 1971-10-21 Bayer Verfahren zur Herstellung von Polyurethanschaumstoffen
DE2552350A1 (de) * 1975-11-21 1977-05-26 Bayer Ag Lagerstabile, carbodiimidgruppen enthaltende polyisocyanate
US4306052A (en) * 1980-09-25 1981-12-15 The Upjohn Company Thermoplastic polyester polyurethanes
DE3516730A1 (de) * 1985-05-09 1986-11-13 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von harnstoff- und/oder biuretgruppen aufweisenden polyisocyanat-zubereitungen, die nach diesem verfahren erhaeltlichen polyisocyanat-zubereitungen und ihre verwendung als isocyanatkomponente bei der herstellung von kunststoffen nach dem isocyanat-polyadditionsverfahren
GB8524579D0 (en) * 1985-10-04 1985-11-06 Polyvinyl Chemicals Inc Coating compositions
US4789791A (en) * 1986-09-26 1988-12-06 Tektronix, Inc. Rotary drive mechanism
GB8705801D0 (en) * 1987-03-11 1987-04-15 Ici Plc Injection moulding compositions
GB8819297D0 (en) * 1988-08-12 1988-09-14 Ici Plc Composite materials

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2259119A1 (fr) * 1974-01-28 1975-08-22 Basf Ag
US4077989A (en) * 1974-07-30 1978-03-07 Bayer Aktiengesellschaft Process for the production of modified polyisocyanates
US4260718A (en) * 1979-12-18 1981-04-07 The Upjohn Company Modified carbodiimide-containing polyisocyanates and glassy polyurethanes therefrom
EP0032011A1 (fr) * 1980-01-02 1981-07-15 Imperial Chemical Industries Plc Mélanges d'isocyanates modifiés
EP0099519A1 (fr) * 1982-07-20 1984-02-01 Bayer Ag Procédé de préparation de matières plastiques à base de polyisocyanates
EP0287947A2 (fr) * 1987-04-24 1988-10-26 Bayer Ag Procédé pour la préparation de revêtements contenant des groupes hydantoine par réaction de composés contenant des groupes carbodiimide avec des acides carboxyliques insaturés

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1088840A1 (fr) * 1999-10-01 2001-04-04 Basf Aktiengesellschaft Masses à couler de polyuréthane transparente, stérilisables à la vapeur, non-cytotoxiques, leur procédé de préparation et leur utilisation, en particulier pour des articles médicaux
EP1088839A1 (fr) * 1999-10-01 2001-04-04 Basf Aktiengesellschaft Masses à couler de polyuréthane transparente, stérilisables à la vapeur, non-cytotoxiques, leur procédé de préparation et leur utilisation, en particulier pour des articles médicaux
EP2998331A1 (fr) * 2014-09-17 2016-03-23 Construction Research & Technology GmbH Polymère organique durcissable comprenant au moins une unité d'acylurée, sa préparation et son utilisation
WO2016041666A1 (fr) * 2014-09-17 2016-03-24 Construction Research & Technology Gmbh Polymère organique durcissable comprenant au moins un motif acylurée, sa préparation et son utilisation
US10590227B2 (en) 2014-09-17 2020-03-17 Construction Research & Technology Gmbh Curable organic polymer comprising at least one acylurea unit, its preparation and use

Also Published As

Publication number Publication date
US5081211A (en) 1992-01-14
AU4082989A (en) 1990-03-15
DK442689D0 (da) 1989-09-07
JPH02107627A (ja) 1990-04-19
DK442689A (da) 1990-03-10
KR900004862A (ko) 1990-04-13
NZ230314A (en) 1991-02-26

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